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| United States Patent |
5,118,346
|
|
Wehner
, et al.
|
June 2, 1992
|
Biocidally active compounds
Abstract
Compounds of the formula
R.sup.1 3Y.sup..sym. R.sup.2 X.sup..crclbar. (I)
in which the radicals R.sup.1 are identical or different and are C.sub.2
-C.sub.6 alkyl, phenyl, C.sub.1 -C.sub.2 alkyl-substituted phenyl or
C.sub.5 -C.sub.7 cycloalkyl, benzyl, tolyl, or hydroxy-C.sub.1 -C.sub.4
alkyl and R.sup.2 is straight-chain or branched C.sub.8 -C.sub.2 alkyl,
and Y is P or N, or R.sup.1 3Y.sup..sym. R.sup.2 is
##STR1##
in which R.sup.4 is H or --CH.sub.3, or
##STR2##
and X is BF.sub.4 or PF.sub.6, which are used as biocides, in particular
in industrial solutions, in paints or in solid materials.
| Inventors:
|
Wehner; Wolfgang (Zwingenberg, DE);
Lorenz; Joachim (Bensheim, DE);
Grade; Reinhardt (Bensheim, DE)
|
| Assignee:
|
Ciba-Geigy Corporation (Ardsley, NY)
|
| Appl. No.:
|
644868 |
| Filed:
|
January 23, 1991 |
Foreign Application Priority Data
| Current U.S. Class: |
106/18.3; 106/18.31; 424/601; 568/9 |
| Intern'l Class: |
C09D 005/16; C07F 009/02 |
| Field of Search: |
106/18.3,18.31
424/601
568/9
|
References Cited
U.S. Patent Documents
| 4038197 | Jul., 1977 | Caspari | 252/46.
|
| 4874526 | Oct., 1989 | Grade | 210/697.
|
| 4976874 | Dec., 1990 | Gannoir et al. | 210/755.
|
| Foreign Patent Documents |
| 063327 | Oct., 1982 | EP.
| |
| 1058618 | Mar., 1954 | FR.
| |
| 61-260259 | Nov., 1986 | JP.
| |
| 994881 | Jun., 1965 | GB.
| |
Other References
Chem. Abstract 92: 25238w (1980).
Chem. Abst. 84: 75119p, 1976, Crivello.
Chem. Abst., vol. 106, 166193x (1987).
CA 107: 177897b.
CA 107: 15534d.
CA 107: 68042y.
|
Primary Examiner: Dixon, Jr.; William R.
Assistant Examiner: Green; Anthony J.
Attorney, Agent or Firm: Villamizar; JoAnn
Parent Case Text
This application is a continuation of application Ser. No. 590,460, filed
Sept. 26, 1990, now abandoned, which is a continuation of Ser. No.
508,518, filed Apr. 9, 1990, now abandoned, which in turn is a
continuation of Ser. No. 317,318, filed Mar. 1, 1989, now abandoned.
Claims
What is claimed is:
1. A composition containing
a) paint and
b) at least one compound of the formula (I)
R.sup.1.sub.3 Y.sup..sym. R.sup.2 X.sup..crclbar. (I)
in which the radicals R.sup.1 are identical or different and are C.sub.2
-C.sub.6 alkyl, phenyl, C.sub.1 -C.sub.2 alkyl-substituted phenyl or
C.sub.5 -C.sub.7 cycloalkyl, benzyl, tolyl or hydroxy-C.sub.1 -C.sub.4
alkyl and R.sup.2 is straight-chain or branched C.sub.8 -C.sub.22 alkyl,
and Y is P and X is BF.sub.4 or PF.sub.6.
2. A composition according to claim 1 wherein X is BF.sub.4.
3. A composition according to claim 1 wherein R.sup.2 is C.sub.10 -C.sub.16
alkyl.
4. A composition according to claim 1 wherein R.sup.2 is C.sub.12 -C.sub.14
alkyl.
5. A composition according to claim 1 wherein R.sup.1 is n-butyl, R.sup.2
is straight or branched chain C.sub.8 -C.sub.22 alkyl, Y is P and X is
BF.sub.4 or PF.sub.6.
6. A composition according to claim 1 wherein said compound of formula (I)
is
(n-C.sub.4 H.sub.9).sub.3 P.sup..sym. (n-C.sub.14
H.sub.29)BF.sub.4.sup..crclbar. or
(n-C.sub.4 H.sub.9).sub.3 P.sup..sym. (n-C.sub.14
H.sub.29)PF.sub.6.sup..crclbar..
7. A composition containing
a) a polymeric material in the form of a building material and
b) at least one compound of the formula (I)
R.sup.1 Y.sup..sym. R.sup.2 X.sup..crclbar. (I)
in which the radicals R.sup.1 are identical or different and are C.sub.2
-C.sub.6 alkyl, phenyl, C.sub.1 -C.sub.2 alkyl-substituted phenyl or
C.sub.5 -C.sub.7 cycloalkyl, benzyl, tolyl or hydroxy-C.sub.1 -C.sub.4
alkyl and R.sup.2 is straight-chain or branched C.sub.8 -C.sub.22 alkyl,
and Y is P and X is BF.sub.4 or PF.sub.6.
Description
The invention relates to novel biocidally active compounds of the
quaternary ammonium and phosphonium base groups.
It is known from FR 1,058,618 that quaternary ammonium fluoborates, such as
dodecyldimethylbenzylammonium fluoborate, can be applied to textile fibres
as agents which prevent rot.
A compound of the type N.sup..sym. Et.sub.2 benzyl C.sub.12 H.sub.25
PF.sub.6.sup..crclbar. is known from JP 61-258,270 as a charge carrier for
electrostatic image development.
GB 994,881 describes quaternary ammoniumfluoborates, for example
n-alkyldimethylbenzylammoniumfluoborates, as catalysts for the manufacture
of heatcuring resins.
Extremely active biocides with a broad biological action spectrum have now
been found, suprisingly, from the series of quaternary ammonium and
phosphonium bases as a cation in association with an anion from the group
of the complex fluorine anions.
The present invention relates to compounds of the formula
R.sup.1.sub.3 Y.sup..sym. R.sup.2 X.sup..crclbar. (I),
in which the radicals R.sup.1 are identical or different and are C.sub.2
-C.sub.6 alkyl, phenyl, C.sub.1 -C.sub.2 alkyl-substituted phenyl or
C.sub.5 -C.sub.7 cycloalkyl, benzyl, tolyl or hydroxy-C.sub.1 -C.sub.4
alkyl and R.sup.2 is straight-chain or branched C.sub.8 -C.sub.22 alkyl,
and Y is P or N, or R.sup.1.sub.3 Y.sup..sym. R.sup.2 is
##STR3##
in which R.sup.4 is --H or --CH.sub.3, or
##STR4##
and X is BF.sub.4 or PF.sub.6, with the proviso, that (C.sub.2
H.sub.5).sub.2 (benzyl)N.sup..sym. (C.sub.12
H.sub.25)PF.sub.6.sup..crclbar. is excluded.
Compounds of the formula I in which R.sup.1 is C.sub.3 -C.sub.6 alkyl and
preferred is i-propyl, n-propyl, n-butyl or is phenyl, cyclohexyl, benzyl
or hydroxyethyl are advantageous.
The invention preferably relates to compounds of the formula I in which Y
is P and the radicals R.sup.1 are identical or different and are i-propyl,
n-butyl, phenyl or cyclohexyl, or Y is N and the radicals R.sup.1 are
identical or different and are n-propyl or n-butyl, or Y is N and the
radicals R.sup.1 are different and are 2-hydroxyethyl and benzyl, and
R.sup.2 is straight-chain or branched C.sub.8 -C.sub.22 alkyl, and X is
BF.sub.4 or PF.sub.6.
In the compounds of the formula I, R.sup.2 is a straight-chain or branched
C.sub.8 -C.sub.22 alkyl radical and can be, for example, n-octyl,
2-ethylhexyl, 1-methylheptyl, 1,1,3-trimethylhexyl, decyl, undecyl,
1-methylundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl or docosyl. The alkyl
radicals having 10 to 16 C atoms are advantageous, thus, for example, the
decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl
radicals, and alkyl radicals having 12 to 14 C atoms are preferred. The
n-dodecyl radical and the n-tetradecyl radical can be regarded as
particularly preferred.
Preferred compounds of the formula I according to the invention are those
in which R.sup.1 is n-butyl.
Other compounds of the formula (I) according to the invention preferably
have the formula
(HOCH.sub.2 CH.sub.2).sub.2 benzyl N.sup..sym. R.sup.2 X.sup..crclbar.
in which R.sup.2 and X are as defined above.
In compounds of the formula (I) according to the invention, X is preferably
BF.sub.4.
Examples of compounds of the formula (I) according to the invention are:
(i-C.sub.3 H.sub.7).sub.3 Y.sup..sym. R.sup.2 X.sup..crclbar.
(i-C.sub.3 H.sub.7).sub.2 (C.sub.6 H.sub.5) Y.sup..sym. R.sup.2
X.sup..crclbar.
(i-C.sub.3 H.sub.7) (C.sub.6 H.sub.5).sub.2 Y.sup..sym. R.sup.2
X.sup..crclbar.
(i-C.sub.4 H.sub.9).sub.3 Y.sup..sym. R.sup.2 X.sup..crclbar.
(i-C.sub.4 H.sub.9).sub.2 (C.sub.6 H.sub.5) Y.sup..sym. R.sup.2
X.sup..crclbar.
(i-C.sub.4 H.sub.9) (C.sub.6 H.sub.5).sub.2 Y.sup..sym. R.sup.2
X.sup..crclbar.
(i-C.sub.3 H.sub.7).sub.2 (C.sub.6 H.sub.5) Y.sup..sym. R.sup.2
X.sup..crclbar.
(i-C.sub.4 H.sub.9).sub.2 (C.sub.6 H.sub.5) Y.sup..sym. R.sup.2
X.sup..crclbar.
(i-C.sub.4 H.sub.9) (C.sub.6 H.sub.5).sub.2 Y.sup..sym. R.sup.2
X.sup..crclbar.
(C.sub.6 H.sub.5).sub.3 Y.sup..sym. R.sup.2 X.sup..crclbar.
(n-C.sub.3 H.sub.7).sub.3 Y.sup..sym. R.sup.2 X.sup..crclbar.
(n-C.sub.3 H.sub.7).sub.2 (n-C.sub.4 H.sub.9) Y.sup..sym. R.sup.2
X.sup..crclbar.
(n-C.sub.3 H.sub.7) (n-C.sub.4 H.sub.9).sub.2 Y.sup..sym. R.sup.2
X.sup..crclbar.
(n-C.sub.4 H.sub.9).sub.3 Y.sup..sym. R.sup.2 X.sup..crclbar.
in which Y, R.sup.2 and X are as defined above. Examples for preferred
compounds are:
(C.sub.2 H.sub.5).sub.3 N.sup..sym. (C.sub.10 -C.sub.14
-Alkyl)BF.sub.4.sup..crclbar., the compound (C.sub.2 H.sub.5).sub.3
N.sup..sym. (n-C.sub.14 H.sub.29)BF.sub.4.sup..crclbar. being particularly
preferred,
(n-C.sub.3 H.sub.7).sub.3 N.sup..sym. (n-C.sub.14
H.sub.29)BF.sub.4.sup..crclbar.,
(n-C.sub.4 H.sub.9).sub.3 P.sup..sym. (n-C.sub.14 H.sub.29)
PF.sub.6.sup..crclbar.,
(C.sub.6 H.sub.5).sub.3 P.sup..sym. (n-C.sub.12 H.sub.25)
BF.sub.4.sup..crclbar.,
(n-C.sub.4 H.sub.9).sub.3 N.sup..sym. (n-C.sub.14 H.sub.29)
PF.sub.6.sup..crclbar.,
(n-C.sub.4 H.sub.9).sub.3 N.sup..sym. (n-C.sub.14 H.sub.29)
BF.sub.4.sup..crclbar.,
(HOCH.sub.2 CH.sub.2).sub.2 (benzyl) N.sup..sym. (n-C.sub.12 H.sub.25)
BF.sub.4.sup..crclbar.,
##STR5##
and, being particularly preferred, the compound of the formula (n-C.sub.4
H.sub.9).sub.3 P.sup..sym. (n-C.sub.14 H.sub.29)BF.sub.4.sup..crclbar..
The compounds according to the invention can be prepared in a manner known
per se.
For example, corresponding ammonium and phosphonium halides are reacted
with metal, for example alkali metal, or with ammonium fluoborates or
phosphates to give the corresponding novel ammonium and phosphonium
fluorine salts according to the invention.
For example, ammonium tetrafluoborate or lead tetrafluoborate or ammonium
hexafluophosphate can be reacted with a quaternary ammonium or phosphonium
halide R.sup.1.sub.3 YR.sup.2 Hal (Hal=halogen). The reaction conditions
here are not critical and the reaction can be carried out, for example,
under normal pressure at room temperature, and for example with water as
the solvent.
The starting materials are likewise known per se and are in some cases
commercially available products.
The compounds according to the invention are excellent biocides and have a
broad biological action spectrum, so that they can be employed generally
for industrial preservation of materials. In particular, they have an
action against bacteria, fungi and algae, protozoa, molluscs, mussels,
balanids, bryozoa, hydroids and the like.
The compounds of the formula I are therefore used according to the
invention as biocides, in particular against the abovementioned organisms,
for example as industrial biocides in the preservation of materials.
The compounds according to the invention are accordingly suitable--as
preservatives for industrial solutions--as additives to building
materials, preferably to mortars, plasters (interior plaster, exterior
plaster, floor pavements and the like) or to mixtures containing hydraulic
binders, such as concrete,--as additive to metalworking liquids,
preferably to drilling and cutting oils, and furthermore also to rolling
mill and forge separating and lubricating substances,--as additive to
coating materials, advantageously to paints and varnishes, preferably to
disperse dyes,--as an active medium in paint films for inhibiting or
preventing rot, so-called anti-fouling paint films, for biocidal finishing
of surface coatings generally and of wood, plastics, polymeric materials,
paper, leather and textiles in particular--for surface treatment of or for
incorporation into building materials and building elements of polymeric
material,--as anti-slime agents in water systems, preferably in systems
for cooling water and also preferably in industrial water, especially in
the cellulose-processing industry, such as the paper industry, and
finally--for disinfection.
A particularly preferred use of the compounds according to the invention is
in anti-fouling paint films, and in this context particularly for paint
films on objects immersed in seawater.
The compounds according to the invention are used in particular in all
instances where objects which are to be protected from the growth of fungi
and algae and attack by balanids, bryozoa, hydroids, molluscs, protozoa,
mussels and bacteria are exposed to seawater. These are, in particular,
hulls of ships, hydraulic structures, buoys and fishing nets, and also
cooling and pipeline systems around or through which seawater flows. The
compounds according to the invention generally protect all materials which
may come into contact with seawater from growth or attack by the
abovementioned organisms, for example wood, cellulose, textiles and
leather, paints, varnishes, for example anti-fouling paints and similar
coating materials, optical glasses and other glasses, plastics, rubber and
adhesives, metals and mineral building materials, as well as other
materials.
The compounds are employed in the concentration ranges known to the expert,
depending on the intended use. The limits of the usable concentrations are
given by the following values: whereas concentrations in the ppm range are
already sufficient in cooling water, concentrations of up to 40% by weight
are usual in anti-fouling formulations.
The compounds can be applied as dusting agents, scattering agents or
misting agents in the pure form or together with carriers. They can also
be dissolved or suspended in liquid media, and if appropriate, wetting
agents or emulsifiers can promote uniform distribution of the active
compound. Other biocides can be added.
A particularly preferred field of use is protective paints, in particular
anti-fouling paints, which contain 0.5-40% by weight, preferably 3 to 15%
by weight, based on the total mixture, of at least one compound of the
formula I in addition to the customary base substances and additives.
the customary base substances for anti-fouling paints are the varnish raw
materials which are called binders and are known to the expert, such as
naturally occurring and synthetic resins, homo- and copolymeric products
of the monomers vinyl chloride, vinylidene chloride, styrene, vinyl
toluene, vinyl esters, vinyl alcohols and acrylic acid and methacrylic
acid and esters thereof, polyester and polyamide resins, and furthermore
chlorinated rubber, naturally occurring and synthetic rubber, which may be
chlorinated or cyclized, and also casting resins, such as epoxy resins and
polyurethane resins, and unsaturated polyesters, which, if appropriate,
can be converted into film-forming higher molecular weight products by
adding of curing agents.
The binders can be liquid or in dissolved form. In the case of dissolved
binders, including thermoplastics, a protective film can also be formed by
evaporating the solvent. Solid coating agents can be applied to objects,
for example, by powder coating processes. Other customary base substances
are, for example, tar, modifiers, dyes, inorganic or organic pigments,
fillers and curing agents.
Finally, the compounds according to the invention can also be used in
elastomeric coatings and in silicone elastomers and fluorine-containing
polymers.
In practice, active compounds are frequently employed in combination with
other biocides. The compounds according to the invention can also be
combined with other biocides. Combinations of products often prove to be
advantageous in anti-fouling paints. The compounds according to the
invention can thus be used, for example, in combination with Cu.sub.2 O,
CuSCN, zinc oxide, triorganotin compounds, such as tributyltin fluoride or
triphenyltin chloride, metallic copper or triazines or generally with
those compounds which are known to the expert as being active against
animal or plant growth.
Another use form of the compounds according to the invention is
incorporation into plastics or naturally occurring or synthetic rubbers,
or application to surfaces of mouldings of these plastics, for example
polyvinyl chlorides and copolymers and mixed polymers thereof,
polyalkylenes, polyacrylates, polystyrenes, copolymers thereof,
polyurethanes or polyisocyantes, polyesters, epoxy resins etc.
Use is particularly appropriate in plastics or polymeric materials which
are used as building materials and, for example, are exposed to
weathering, or are employed in the region of humid or wet areas. Examples
which may be mentioned here are roofing materials or linings of polyvinyl
chloride, butyl rubber, chlorinated polyethylene, polyisobutylene,
chloroprene and chloroisoprene, EPDM and PVC copolymers with vinyl acetate
or ethyl vinyl acetate, polyacrylonitrile-styrene, if appropriate mixed
with fibrous fillers (if appropriate, also blended with bitumen), or
foamed polyvinyl chlorides or polystyrenes, as insulating materials
against heat and cold.
The compounds according to the invention are suitable both for the uses
mentioned and for other uses. They are not hygroscopic, are stable to heat
and have a very low water solubility.
The invention also relates to compositions containing at least one compound
of the formula I according to the present invention. The form and nature
of the particular composition containing the compound according to the
invention depends on the intended use.
Compounds being preferred or being particularly preferred, as mentioned
above, lead to compositions being preferred or being particularly
preferred.
The compounds of the formula I can be in the following finished forms for
application (the percentage by weight data in parentheses represent
advantageous amounts of active compound):
Solid finished forms
Dusting agents and scattering agents (up to 10%), granules, coated
granules, impregnated granules and homogeneous granules, pellets (grains)
(1 to 80%).
Liquid finished forms
a) water-dispersible active compound concentrates: Wettable powders and
pastes (25-90% in the commercial pack, 0.01 to 15% in the ready-to-use
solution), emulsion and solution concentrates (10 to 50%; 0.01 to 15% in
the ready-to-use solution);
b) Organic solutions (0.1 to 20%); aerosols.
The invention thus furthermore relates to agents containing the compounds
according to the invention and to the use of the compounds and agents
according to the invention for combating harmful organisms, for example
bacteria, fungi, algae, protozoa, molluscs, mussels, balanids, bryozoa,
hydroids and the like, in particular in the preservation of materials.
The biocidal agents according to the invention can also contain other
active substances.
Examples of these are:
a) Organosulphur compounds, for example methylene dithiocyanate (MBT),
isothiazolones or 3,5-dimethyltetrahydro-1,3,5-2H-thiodiazine-2-thione
(DMTT). Such substances are used, in particular, against slime formation
in papermaking.
b) Chlorinated phenols, such as sodium pentachlorophenolate. Such compounds
are distinguished by a very broad action spectrum.
c) Copper salts, such as copper sulphate and copper nitrate as additional
algicides.
d) 2,2-Dibromo-3-nitrilopropionamide (DBNPA) as an algicide, fungicide and
bactericide.
e) Chlorine and bromine as algicides and bactericides, which are used in
particular in water treatment.
f) Chlorine dioxide, chlorine isocyanurates and hypochlorites as biocides,
for example in water treatment.
g) Triazines, for example
2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, in particular
as algicides.
h) Triorganotin compounds, for example bis(tributyltin) oxide (TBTO), in
particular as molluscicides, fungicides and algicides.
i) Wood biocide
ia) Salt mixtures based on silicofluorides, hydrogenfluorides, inorganic
boron compounds, chromates, fluorides, arsenic (oxide, arsenates), copper
salts (sulphate, naphthenate), salts of tin and zinc and mercury
compounds.
ib) Tar oil preparations
ic) Organic active compounds, such as pentachlorophenol, phenol, DDT,
dieldrin, lindane, Gammexane, chlorinated naphthalenes, dichlofluanid,
tributyltin compounds, pyrethroids, 3-iodo-2-propenyl N-butylcarbamate and
furmecyclox.
j) Disinfectants
ja) Phenol or phenol derivatives
jb) Formaldehyde and/or other aldehydes and derivatives
jc) Chlorine and organic or inorganic substances containing active chlorine
jd) Amphotensides
je) Quaternary onium compounds.
Of course, such formulations can moreover also contain other substances and
auxiliaries, such as are usually co-used in such formulations. These
include, for example, cationic or nonionic surface-active substances,
electrolytes, complexing agents, solubilizing agents and dyes and
fragrences. These additives are used, for example, for improving the
wetting ability and curing stability, for adjusting the viscosity and for
increasing the stability of the solutions to low temperatures.
When used in emulsion paints and plasters, the compounds according to the
invention can be combined with another fungicide. Combinations with a
bactericide are possible in water treatment, in order to combat
slime-forming bacteria. Such combinations can bring technological
advantages. In many cases combination with other algicides is also
advantageous.
The invention also relates to compositions containing a) a paint and b) an
effective amount of at least one compound of the formula (I) according to
the present invention.
The following examples illustrate the invention in more detail without
limiting its scope. Percentages (%) quoted therein are percentages by
weight and parts are parts by weight.
EXAMPLES
1. Tri-n-butyl-n-tetradecylphosphonium tetrafluoborate
2,176 g of a 50% strength solution of tri-n-butyl-n-tetradecylphosphonium
chloride in water are added dropwise to 314.5 g (3.0 mol) of ammonium
tetrafluoborate in 5 of H.sub.2 O at 2.degree. C., with vigorous stirring,
a thick precipitate forming. After the mixture has been left to settle for
a short time, the precipitate is filtered off with suction, rinsed with 3
portions of 500 ml of water and dried to constant weight over P.sub.2
O.sub.5.
Yield: 1,192 g, corresponding to 98% of theory--melting point: 39.degree.
C.
2. Tri-n-butyl-n-tetradecylphosphonium hexafluophosphate
The preparation is analogous to Example 1, except that an equivalent amount
of a 50% strength aqueous ammoniumhexafluophosphate solution is used.
Yield: 80%--melting point: 41.degree. C.
3. Triphenyl-n-dodecylphosphonium tetrafluoborate
5.5 g (0.00715 mol) of a 50% strength aqueous solution of lead
tetrafluoborate are added to 22.3 g (0.0143 mol) of a 30% strength aqueous
solution of triphenyl-n-dodecylphosphonium chloride, while stirring. The
precipitate formed is digested with 250 ml of methanol, the lead chloride
is filtered off and the methanolic solution is concentrated to a residue.
Yield: quantitative--yellow, highly viscous oil, n.sub.D.sup.20 =1.5414.
4. Tri-n-butyl-n-tetradecylammonium hexafluophosphate
A solution of 3.3 g (0.02 mol) of ammonium hexafluophosphate in 20 ml of
water is added to a solution of 9.3 g (0.02 mol) of
tri-n-butyl-n-tetradecylammonium bromide in 50 ml of water, while
stirring. The precipitate formed is filtered off, washed and concentrated
to a residue.
Yield: 85% of theory--melting point: 104.degree. C.
5. Tri-n-butyl-n-tetradecylammonium tetrafluoborate
7.6 g (0.01 mol) of 50% strength lead tetrafluoborate solution are added to
a solution of 9.3 g (0.02 mol) of tri-n-butyl-n-tetradecylammonium bromide
in 50 ml of water, while stirring. The precipitate is decocted with
isopropanol and the lead bromide is separated off. The filtrate is then
concentrated to a residue.
Yield: 70%--melting point: 88.degree. C.
6. Bis(hydroxyethyl)benzyl-n-dodecylammonium tetrafluoborate
16.8 g (0.16 mol) of ammonium tetrafluoborate in 200 ml of water are added
to 49.5 g (0.124 mol) of bis(hydroxyethyl)benzyl-n-dodecylammonium
chloride in 500 ml of water, while stirring, during which an oil separates
out, which is taken up in 200 ml of ethyl acetate, the mixture being
washed several times with water. After drying, the mixture is concentrated
to a residue.
Yield: 95% of theory--pale yellow viscous oil, n.sub.D.sup.22 =1.4812.
EXAMPLE 7
Preparation of the Compounds of the Formula [(C.sub.2 H.sub.5).sub.3
N(.sup.n C.sub.12 H.sub.25)].sup..sym. BF.sub.4.sup..crclbar..
0.06 mol (6.3 g) of ammonium fluoborate in 100 ml of water is added
dropwise to a solution of 0.06 mol (21.0 g) of triethyllaurylammonium
bromide in 250 ml of water, while stirring. The precipitate formed is
filtered off with suction, washed free from bromide and dried to constant
weight.
Yield: 21.1 g (98.6% of theory)--melting point: 127.degree.-128.degree. C.
The following N.sup..sym. BF.sub.4.sup..crclbar. salts are obtained
analogously to Example 7:
__________________________________________________________________________
Yield
Melting
Example
N.sup..sym. [%] point [.degree.C.]
Comments
__________________________________________________________________________
8 (C.sub.2 H.sub.5).sub.3 N(.sup.n C.sub.14 H.sub.29)
96.9
146-147
9 (C.sub.2 H.sub.5).sub.3 N(.sup.n C.sub.18 H.sub.37)
93.7
168-171 ammonium bromide dis-
solved in water/metha-
nol*)
10 (.sup.n C.sub.3 H.sub.7).sub.3 N(.sup.n C.sub.14 H.sub.29)
93.5
69-70
11 (C.sub.2 H.sub.5).sub.3 N(.sup.n C.sub.8 H.sub.17)
67.8
89-91 the oil which separ-
ates is extracted with
ethyl acetate and the
extract is washed free
from bromide and con-
centrated to a residue
12 (C.sub.2 H.sub.5).sub.3 N(.sup.n C.sub.10 H.sub.21)
80.2
105-107 precipitation is
carried out at +3.degree. C.
13 (C.sub.2 H.sub.5 ).sub.3 N(.sup.n C.sub.16 H.sub.33)
91.3
160-161 ammonium bromide dis-
dolved in water/metha-
nol*)
14
##STR6## 93.5
56-58 ammonium bromide dis- dolved in
water/metha- nol*)
15
##STR7## 95.2
viscous oil (n.sub.D.sup.20 = 1.4762)
ammonium bromide dis- solved in
water/metha- nol*), the oil
which separates out is taken up in ethyl
acetate and the mixture is washed free
from bromide and concen- trated to a
residue.
__________________________________________________________________________
*) Just enough methanol is added to the aqueous suspension for a clear
solution to result.
EXAMPLE 16
Determination of the Minimum Inhibitory Concentration against Bacteria
The ONCs (overnight-incubated cultures), washed in Caso peptone broth
(Merck), of the various bacteria strains: A) Proteus vulgaris, B)
Pseudomonas aeruginosa, C) Enterobacter aerogenes, D) Serratia marcesens,
E) Alcaligenes denitrificans and F) Bacillus subtilis, are in each case
diluted 1/1,000 in saline. An amount of the suspension is introduced into
Caso peptone broth such that the bacteria are diluted again to 1/1,000.
The compounds shown in Table 1 are then added in each case in amounts of
30, 100 and 300 mg/1. After incubation at 30.degree. C. for 24 hours in a
shaking water bath, the mixtures are evaluated according to their
turbidity. The minimum inhibitory concentration (MIC) is the concentration
at which the broth does not become turbid due to bacterial growth.
The results are illustrated in the following Table 1:
TABLE 1
______________________________________
Determination of the MIC against bacteria
(concentration in g/l)
Compound Strain
from example
A B C D E F
______________________________________
1 30 100 30 30 30 30
3 30 30 30 30 30 30
5 30 300 30 30 30 30
6 30 100 100 100 30 30
7 300 >300 >300 300 >300 30
8 30 300 30 100 30 30
9 30 >300 >300 >300 >300 30
10 30 >300 100 100 100 30
13 30 >300 30 30 300 30
14 100 300 300 300 100 30
15 100 300 100 300 100 100
______________________________________
The good growth-inhibiting action of the compounds even against the
Gram-negative bacteria which are difficult to combat can be seen from
Table 1.
EXAMPLE 17
Determination of the Minimum Inhibitory Concentration (MIC) against Fungi
Strains: A) Aspergillus niger, B) Sacharomyces cerevisiae, C) Penicillium
funiculosum, D) Chaetomium globosum, E) Aureobasidium pullulans and F)
Coniophora puteana.
The investigation is carried out by the known agar incorporation test in
malt extract agar (Merck). For the inhibition, the various compounds are
in each case added in an amount such that concentrations of 10, 50 and 100
mg/1 result in the agar. The concentrations (mg/1) required for inhibiting
the growth of the fungi (starting from fungus spores dripped on) are
illustrated in Table 2.
TABLE 2
______________________________________
Determination of the MIC against fungi
(concentration in mg/l)
Compound Strain
from example
A B C D E F
______________________________________
5 100 50 50 50 50 100
1 50 10 10 10 50 10
3 100 50 10 50 10 50
2 100 10 10 100 50 100
6 >100 50 10 50 10 50
7 >100 >100 50 100 50 50
8 50 100 10 50 10 50
9 >100 >100 50 50 50 50
10 100 100 50 50 10 10
13 100 100 10 100 50 10
14 >100 >100 50 100 10 50
15 >100 100 10 50 50 10
______________________________________
concentration tested: 10, 50, 100 mg/l.
It can be seen from Table 2 that the compounds are also outstanding
fungicides.
EXAMPLE 18
Use of the Compounds as Anti-fouling Biocides
To test the activity against growth on objects immersed in the sea, the
compound according to Example 1 is incorporated into anti-fouling paints.
An anti-fouling paint such as is known to the expert and which is based on
vinyl chloride copolymer/rosin (2/1 part by weight) with a pigment volume
concentration of about 40%, and a second anti-fouling paint of similar
make-up but with a higher rosin content (vinyl chloride
copolymer/rosin=1/1) are prepared. The compound according to Example 1 is
incorporated into these paints, the paint is brushed onto specimen sheets
and, after drying (10 days), the sheets are suspended in the North Sea.
The corresponding paints but without adding of the product are exposed in
the same way for comparison. On a rating scale of 0 (=completely covered
with growth) to 10 (=completely free from growth), the following results
are obtained after exposure for 61/2 weeks (growth by hydroids=HY; growth
by barnacles=BA):
Vinyl/rosin 2:1: without additive HY 5, BA 5
Vinyl/rosin 2:1: with additive HY 8, BA 8
Vinyl/rosin 1:1: without additive HY 0, BA 0
Vinyl/rosin 1:1: with additive HY 4, BA 10.
EXAMPLE 19
Use as an Algicide in Polymeric Material
To test the activity against attack by algae, various concentrations, which
can be seen from Table 3, of the compound according to Example 1 are
incorporated into roof sheeting consisting of polyisobutylene. A roof
sheeting without biocide is investigated as a comparison.
A 1 cm.sup.2 piece of film from each test strip is kept in water for 5
days, in each case placed on an algae agar plate and inoculated with 0.1
ml of a 1+1+1 mixture of 14-day cultures of the algae Chlorella vulgaris
and Chlorella spec. (isolated from damage cases in practice) and
Scenedesmus obliques, which had been diluted 1/10 in saline.
After 3 weeks, the plates are evaluated and the films are placed in fresh
agar and inoculated again.
Evaluation of the growth after 3 and 6 weeks under artificial light is
performed in accordance with the following scheme.
1=growth on the film
2=partial growth on the film
3=growth up to the edge of the film
4=inhibiting aerola around the film <5 mm
5=inhibiting aerola around the film >5 mm
The following result is obtained:
TABLE 3
______________________________________
algae growth after
3 6 weeks
______________________________________
Film with addition of the
0,1 4 4
compound according to 0,5 4 4
Example 1 in % by weight 1 4 4
Comparison film without addition
2-3 2
______________________________________
EXAMPLE 20
Example 19 is repeated, except that instead of the stated concentrations of
compound according to Example 1 alone, a combination of 1% by weight of
the compound according to Example 1 and 0.07% by weight of
2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine is used. The
results obtained can be seen from Table 4.
TABLE 4
______________________________________
algae growth after
3 6 weeks
______________________________________
Film with addition of 1% of the
5 5
compound according to Example 1 +
0.07% of 2-methylthio-4-t-
butylamino-6-cyclopropylamino-s-
triazine
Comparison form without addition
2-3 2
______________________________________
EXAMPLE 21
Use as a Fungicide in Wood
Determination of the limit of the activity against wood-destroying
Basidiomycetes bred on agar (in accordance with EN 113). The test methods
described in this European Standard is a laboratory method which forms a
basis for evaluation of the activity of a wood preservative against
wood-destroying Basidiomycetes. It allows determination of the limit
concentration from which a susceptible type of wood can be regarded as
being adequately protected after impregnation under the experimental
conditions.
TEST FUNGI
The test fungi are listed below:
Coniophora puteana (Schumacher ex Fries) Karsten, strain FPRL 11E, for soft
timbers=strain 91,
Poria placenta (Fries) Cooke sensu. J. Eriksson, strain SPRL 280, for soft
timbers=strain 96,
Gloeophyllum trabeum (Persoon ex Fries) Murrill, strain BAM up to 109, for
soft timbers=strain 94,
Breeding of the strain and composition of the nutrient medium were as
described in EN 113.
Solutions of isopropanol/water (1:1) containing 0.2%, 0.5%, 1%, 2% and 5%
of active substance according to Example 1 are prepared.
The specimen woods of pine, nominal dimensions: 50 mm.times.25 mm.times.15
mm, are obtained and prepared as described in EN 113.
The impregnation according to EN 113 ensures complete thorough impregnation
of the specimen woods with the wood preservative solution.
The amount of preservative absorbed is converted into weight per unit
volume of the wood.
After impregnation the specimen woods are dried for 4 weeks, conditioned
and, for sterilization, sterilized in films using electrons (beam energy
2.5 MeV, minimum dose 25 kGy).
The actual fungus experiment is carried out as described in EN 113
(duration of experiment 16 weeks).
At the end of the experiment, the specimen woods are removed from the
experimental vessels and freed from adhering fungus mycelium.
The limit of the activity of a wood preservative is determined by the two
amounts of wood preservative which correspond to
the lowest concentration which preserves the wood and
the next lowest concentration in the series, at which the wood is no longer
adequately preserved.
The protection achieved by the wood preservative is regarded as being
adequate for a given concentration if
the mean corrected loss in weight of the specimen woods is less than 3% and
not more than one specimen wood shows a loss in weight of more than 3% but
less than 5%.
The limit of the activity is given for each species of fungus by the
limiting values in kg of preservative per m.sup.3 of wood. The
corresponding concentrations of the preservative in the particular solvent
or diluent are stated.
______________________________________
Effective Take-up
Strain No. concentration (%)
kg/m.sup.3
______________________________________
Coniophora puteana
91 0.5-1.0 >3.0-<6.0
FRRL 11 E
Poria placenta
96 1.0-2.0 >5.0-<10.0
FRRL 280
Gleophyllum trabeum
94 .ltoreq.0.2 .ltoreq.1.0
BAM, EbW 109
______________________________________
As can be seen from the table, the active substance according to Example 1
is highly effective against the wood-destroying fungi investigated here.
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